High-performance photocatalytic metal-organic framework antibacterial material, preparation method therefor, and use thereof

Abstract

The present invention relates to the technical field of metal-organic framework materials, and in particular to a high-performance photocatalytic metal-organic framework (MOF) antibacterial material, a preparation method therefor, and a use thereof. The preparation method comprises: adding p-toluenesulfonic acid, tris(4-aminophenyl)amine, and Cu3L into a polyethylene glycol solution; performing stirring for uniform mixing and then heating for reaction; collecting the resulting precipitate by centrifugation and washing same; and drying the precipitate to obtain GZHMU-2 powder. The GZHMU-2 having a high-performance photocatalytic MOF antibacterial material is synthesized by means of a condensation reaction of an aldehyde and an amine. Under irradiation, the GZHMU-2 can generate active oxygen by means of a photocatalytic effect, thereby achieving an antibacterial effect. The GZHMU-2 has a killing effect on Escherichia coli (EC) and Staphylococcus aureus (SA), and is prepared into an antibacterial film by means of hot pressing. When the antibacterial film is applied to masks, targeted and efficient killing of EC and SA can be achieved, thereby achieving effective protection of persons wearing the masks.

Description

A high-performance photocatalytic metal-organic framework antibacterial material and its preparation method and application Technical Field

[0001] The present invention belongs to the technical field of metal organic framework materials, and in particular relates to a high-performance photocatalytic metal organic framework antibacterial material and a preparation method and application thereof. Background Art

[0002] Infectious pathogens such as drug-resistant bacteria, fungi, and viruses pose a serious global public health concern and can threaten human health. Developing protective measures against biological threats is particularly important, especially as public health emergencies and emerging diseases caused by unknown microorganisms complicate the development of protective technologies. These pathogens can be released through sneezing, coughing, and other means as droplets carrying pathogens, rapidly infecting susceptible individuals. They can also form aerosols that remain in the air for long periods of time before being inhaled into the respiratory tract, causing infection. Furthermore, these pathogens can survive on fabrics for days, increasing the risk of infection. Given this challenge, researchers are interested in developing protective film materials that reduce microbial contamination and the spread of microbial infections. The development of photocatalytic self-cleaning materials, in particular, offers an attractive avenue for preventing contamination. During the photodynamic antibacterial process, bacteria cannot resist the bactericidal effect of reactive oxygen species by stopping the uptake of photosensitizer small molecules, increasing the metabolic detoxification rate, or accelerating the excretion of photosensitizer small molecules. Therefore, photodynamic antibacterial is less likely to cause the body to develop drug resistance than traditional antibacterial methods. In addition, only bacteria exposed to light sources will be inhibited during the antibacterial process, and it will not affect the body's normal bacterial flora system, greatly improving the safety and directionality of antibacterial treatment.

[0003] Photocatalytic antimicrobial materials have become promising biocides due to their ability to generate reactive oxygen species (ROS) upon irradiation. However, most commercially available photocatalytic antimicrobials, such as TiO2-based materials, require high-energy ultraviolet (UV) light irradiation to generate ROS. Although some visible-light photocatalysts have been developed, the antimicrobial efficiency of these materials still needs to be improved before they can be widely adopted. Metal-organic frameworks (MOFs) are emerging porous crystalline materials constructed from metal ions and organic ligands through coordination bonds. MOFs possess unique advantages in adsorption, photocatalysis, and biomedical materials due to their porosity, large surface area, and multiple metal sites. Specifically in photocatalytic antibacterial and antiviral properties, MOFs offer the following advantages over traditional metal oxides: ① Rational design of organic ligands can tune the material's visible light absorption spectrum; ② Organic ligands can effectively separate metal nodes, thereby increasing the utilization of active sites; and ③ The porous and large surface area structure facilitates the diffusion of reactive oxygen species, thereby improving the efficiency of their generation. Currently, most masks only block microorganisms but lack the ability to effectively kill pathogens, resulting in a short service life. Furthermore, pathogens can survive on fabric for days, increasing the risk of infection. While there have been reports of MOF photocatalytic sterilization masks, the concentration of sterilizing materials used is high, and most MOFs have a narrow visible light absorption spectrum, significantly reducing visible light utilization and requiring a higher-intensity light source.

[0004] Summary of the Invention

[0005] In view of the above problems, the object of the present invention is to provide a high-performance photocatalytic metal-organic framework antibacterial material and its preparation method and application.

[0006] The technical contents of the present invention are as follows:

[0007] The present invention provides a method for preparing a high-performance photocatalytic metal-organic framework antibacterial material, comprising the following steps:

[0008] p-Toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L were added to the polyethylene glycol solution, stirred and mixed, and then heated to react. The resulting precipitate was collected by centrifugation, washed, and dried to obtain GZHMU-2 powder;

[0009] The mass ratio of toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L is (4-5.5):1:(1-2), preferably 5.5:1:1.75;

[0010] The solid-liquid ratio of the mixture of p-toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L to polyethylene glycol is (30-40):1 mg / mL;

[0011] The polyethylene glycol solution includes one or more MVs of 200 to 1000;

[0012] Preferably, at least one of PEG (MV200), PEG (MV400), and PEG (MV1000) is included;

[0013] Furthermore, the polyethylene glycol solution is preferably a mixture of PEG (MV400) and PEG (MV1000), which are used in a volume ratio of (1-2): (1-2);

[0014] The heating reaction temperature is 150°C to 200°C and the time is 15 to 30 minutes;

[0015] The washing reagents include tetrahydrofuran, deionized water and DMF;

[0016] The structure of GZHMU-2 is

[0017] The synthesis of Cu3L is based on the paper Angew.Chem.Int.Ed.2023,62,e202302808: 1H-pyrazole-4-carboxaldehyde and copper nitrate in a mass ratio of 1:(1.5-2) were dissolved in deionized water, an organic solvent was added, and an oil bath reaction was carried out. The blue color faded, and Cu3L was obtained by filtration and washing.

[0018] The amount of the organic solution is 67 mL, including DMF and anhydrous ethanol;

[0019] The temperature of the oil bath reaction is 110°C;

[0020] The structure of Cu3L is

[0021] The present invention also provides a high-performance photocatalytic metal organic framework antibacterial material, which is the GZHMU-2 material prepared by the above preparation process, and its structure is It is a metal-organic framework structure obtained by the condensation reaction of aldehydes and amines. Studies on its antibacterial mechanism have shown that under light, GZHMU-2 can produce active oxygen through photocatalysis, thereby playing an antibacterial role.

[0022] The present invention also provides an application of a high-performance photocatalytic metal-organic framework antibacterial material, wherein the metal-organic framework antibacterial material is used to prepare antibacterial consumables, including masks, protective clothing, etc.

[0023] Its application method is:

[0024] p-Toluenesulfonic acid, tris(4-aminophenyl)amine, and Cu3L were sequentially added to polyethylene glycol (PEG 200) and stirred at room temperature. The resulting solution was evenly applied to a support twice, hot-pressed at high temperature, cooled, and washed with deionized water to obtain an antibacterial film rich in GZHMU-2.

[0025] The mass ratio of toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L is (4-5.5):1:(1-2), preferably 4:1:1.2;

[0026] The solid-liquid ratio of the mixture of p-toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L to polyethylene glycol is (30-40):1 mg / mL;

[0027] The carrier comprises non-woven fabric NWF;

[0028] The high temperature hot pressing is performed at a hot pressing temperature of 150 to 200° C. for 15 to 30 minutes;

[0029] Furthermore, the hot pressing temperature is preferably 170-175°C.

[0030] When the antibacterial consumable is a mask, the antibacterial film rich in GZHMU-2 is combined according to the required structure of the mask, including the following structure:

[0031] The mask comprises a fixing strap, a nose clip and a mask body;

[0032] The mask body has a composite layer structure consisting of a non-woven fabric outer layer, a middle layer and a non-woven fabric inner layer, wherein the middle layer is an antibacterial film rich in GZHMU-2 formed by loading on the non-woven fabric.

[0033] The beneficial effects of the present invention are as follows:

[0034] The preparation process of the high-performance photocatalytic metal-organic framework antibacterial material GZHMU-2 of the present invention is to synthesize GZHMU-2 with high-performance photocatalytic MOF antibacterial material through the condensation reaction of aldehyde and amine. Under light, GZHMU-2 can produce active oxygen through photocatalysis, thereby playing an antibacterial role, and has a killing effect on Escherichia coli (EC) and Staphylococcus aureus (SA);

[0035] The MOF material GZHMU-2 of the present invention is prepared into an antibacterial film by hot pressing and applied to a mask, which can achieve targeted and efficient sterilization of Escherichia coli and Staphylococcus aureus by the mask, thereby achieving effective protection for the wearer. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG1 is a synthesis process diagram of Cu3L material in Example 1;

[0037] FIG2 is a diagram showing the synthesis process of GZHMU-2 powder in Example 1;

[0038] FIG3 is a graph showing the photocatalytic bactericidal activity of GZHMU-2 powder in Example 1;

[0039] FIG4 is a schematic diagram of the synthesis process of the GZHMU-2 antibacterial film of Example 3;

[0040] Figure 5 is an optical imaging diagram of the GZHMU-2 / NWF mask of Example 4;

[0041] FIG6 is an XRD pattern of GZHMU-2 powder and loaded GZHMU-2 / NWF of the present invention;

[0042] FIG7 is a SEM image of GZHMU-2 / NWF loaded in the present invention;

[0043] FIG8 is a graph showing the difference in bacterial morphology observed with and without GZHMU-2 photocatalytic sterilization under low-voltage transmission electron microscopy;

[0044] FIG9 is a fluorescence staining image of bacteria with and without GZHMU-2 photocatalytic sterilization observed under a fluorescence microscope;

[0045] Figure 10 shows pictures of bacterial growth on NWF and GZHMU-2 / NWF cloth;

[0046] Figure 11 shows a picture of bacterial growth on the GZHMU-2 / NWF mask;

[0047] Figure 12 is a schematic diagram of the synthesis process of JN1 and JN2 materials;

[0048] FIG13 is a comparative picture of the antibacterial efficiency of GZHMU-2 of the present invention and other MOF materials;

[0049] FIG14 is a graph showing active oxygen species determined by EPR for GZHMU-2 and other MOF materials of the present invention. DETAILED DESCRIPTION

[0050] The present invention is further described in detail below through specific implementation cases and accompanying drawings. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. After reading the present invention, various equivalent modifications of the present invention by those skilled in the art are all within the scope of the claims attached to this application.

[0051] Unless otherwise specified, all raw materials and reagents in the present invention are raw materials and reagents from conventional markets.

[0052] Example 1

[0053] A high-performance photocatalytic metal-organic framework antibacterial material

[0054] 1) Synthesis of Cu3L (reference paper Angew. Chem. Int. Ed. 2023, 62, e202302808): Dissolve 2.0 g of 1H-pyrazole-4-carboxaldehyde and 4.0 g of copper nitrate in 51 mL of deionized water, add 67 mL of DMF and anhydrous ethanol, and incubate in an oil bath at 110°C until the blue color fades. Filter and wash to obtain the product.

[0055] Its synthesis process is shown in Figure 1;

[0056] 2) Synthesis of GZHMU-2: 0.44 g of p-toluenesulfonic acid, 80 mg of tris(4-aminophenyl)amine, and 0.14 g of Cu3L were added to 20 mL of polyethylene glycol (PEG) (MV:400:1000), stirred and mixed, and reacted at 170° for 30 min. The resulting precipitate was collected by centrifugation, washed with tetrahydrofuran, deionized water, and DMF, and dried to obtain GZHMU-2 powder.

[0057] The synthesis process is shown in Figure 2.

[0058] The photocatalytic bactericidal activity of the GZHMU-2 powder from Example 1 was investigated using Gram-negative Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as model bacteria. The bactericidal efficiency was measured using plate colony counts under both light and dark conditions. The results, shown in Figure 3, show that under light conditions, the GZHMU-2 powder effectively killed E. coli and S. aureus, achieving an antibacterial rate of 99.99% at a concentration of 100 μg / mL.

[0059] Example 2

[0060] A high-performance photocatalytic metal-organic framework antibacterial material

[0061] 1) Synthesis of Cu3L: Dissolve 1.9 g of 1H-pyrazole-4-carboxaldehyde and 3.7 g of copper nitrate in 49 mL of deionized water, add 65 mL of DMF and anhydrous ethanol, and incubate in an oil bath at 110°C until the blue color fades. Filter and wash to obtain the product.

[0062] 2) Synthesis of GZHMU-2: 0.44 g of p-toluenesulfonic acid, 80 mg of tris(4-aminophenyl)amine, and 0.14 g of Cu3L were added to 20 mL of polyethylene glycol (PEG:MV:400:1000). The mixture was stirred and reacted at 170°C for 30 min. The resulting precipitate was collected by centrifugation, washed with tetrahydrofuran, deionized water, and DMF, and dried to obtain GZHMU-2 powder.

[0063] Example 3

[0064] A high-performance photocatalytic metal-organic framework antibacterial material for antibacterial consumables

[0065] 0.44 g of p-toluenesulfonic acid, 80 mg of tris(4-aminophenyl)amine, and 0.14 g of Cu3L were added sequentially to 20 mL of polyethylene glycol (PEG 200), stirred at room temperature for 1 h, and the above solution was evenly applied on NWF twice. The mixture was hot-pressed at 170 °C for 15 to 30 min, cooled, and washed with deionized water to obtain an antibacterial film rich in GZHMU-2. The synthesis process is shown in Figure 4.

[0066] Example 4

[0067] An antibacterial mask

[0068] Including fixing strap, nose clip and mask body;

[0069] The mask body consists of a non-woven fabric outer layer, an antibacterial film rich in GZHMU-2 (middle layer) prepared in Example 3, and a non-woven fabric inner layer, namely a GZHMU-2 / NWF mask. FIG5 is an optical imaging image of the mask, which reflects a three-layer structure.

[0070] The GZHMU-2 powder from Example 1 and the antibacterial film from Example 3 were characterized by X-ray diffraction (XRD) using a Bruker D8 Advance (Bruker, Germany) instrument at 40 kV and 40 mA. As shown in Figure 6, the diffraction peaks of the antibacterial film correspond exactly to those of GZHMU-2. The XRD results confirm that GZHMU-2 was successfully grown in situ on the nonwoven fabric.

[0071] The antibacterial film of Example 3 was examined using a Czech-made scanning electron microscope (MARA3) under the following conditions: accelerating voltage 40 kV, current 5 mA. The results, shown in Figure 7, demonstrate uniform in-situ growth of GZHMU-2 nanoparticles on the nonwoven fabric.

[0072] The NWF loaded with GZHMU-2 material and the NWF without GZHMU-2 material were cut into (30±2) mm×(30±2) mm, respectively, soaked in 75% ethanol solution for 5 min, and then dried at 40°C.

[0073] The cut NWF loaded with GZHMU-2 material and the NWF without GZHMU-2 material were placed in sterilized culture dishes, and a sterile glass slide of (30±2) mm×(30±2) mm in size was placed in the dish. 0.45 mL of the experimental Escherichia coli suspension (5×10 5 ~1×106 CFU / mL) were evenly coated on NWF loaded with GZHMU-2 material and NWF not loaded with GZHMU-2 material, and covered with a sterile glass slide of (30±2) mm×(30±2) mm. The NWF loaded with GZHMU-2 material was irradiated with simulated sunlight (300W Xe lamp plus AM 1.5 filter and attenuator) at a density of 100 mW / cm for 30 min. After the photocatalytic disinfection reaction was completed and eluted, the colonies in the culture dish were incubated at 37°C for 20 h, and the colonies were counted.

[0074] Calculate bacterial survival rate: Survival rate = C / C0;

[0075] C0: number of colony growth without GZHMU-2 material treatment;

[0076] C: Number of colony growth after treatment with GZHMU-2 material;

[0077] Calculations show that the killing rate of NWF loaded with GZHMU-2 material against E. coli reaches over 99.99%;

[0078] Escherichia coli suspension (5×10 5 ~1×10 6 CFU / mL) was replaced with Staphylococcus aureus suspension (5×10 5 ~1×10 6 CFU / mL), and other test conditions remained unchanged. It was calculated that the killing rate of NWF loaded with GZHMU-2 material against Staphylococcus aureus reached more than 99.99%.

[0079] The difference in bacterial morphology with and without GZHMU-2 photocatalytic sterilization was observed using a low-voltage transmission electron microscope. The results are shown in Figure 8. After being treated with GZHMU-2 material, the bacterial outer mold was severely wrinkled, damaged, and even broken.

[0080] Fluorescence microscopy was used to observe the inactivation of bacteria with and without GZHMU-2 photocatalytic sterilization. The results are shown in Figure 9. After the GZHMU-2 material was treated with light, the red fluorescence was significantly enhanced, indicating that the cell membrane was destroyed.

[0081] The NWF and GZHMU-2 / NWF were edge-sealed at 200° using an electric vulcanizing molding machine (BL-6170-A) and shaped at room temperature to prepare GZHMU-2 / NWF masks. The bacterial solution was atomized using an atomizer, with the atomizer outlet section 10 cm away from the mask. 7A CFU / mL E. coli suspension was sprayed onto the mask at a flow rate of 0.2 mL / min for 5 minutes. The GZHMU-2 / NWF mask was exposed to simulated sunlight for 30 minutes. Each layer of the MOFilter mask was fully eluted with 10 mL of 0.9% saline solution and incubated at 37°C for 20 hours to count the colonies in the culture dish.

[0082] Same as above E. coli suspension 10 7 CFU / mL was replaced by Staphylococcus aureus, and the results showed that there was no growth of Escherichia coli and Staphylococcus aureus on GZHMU-2 / NWF.

[0083] As shown in Figure 10 , the bacterial growth on NWF and GZHMU-2 / NWF cloths showed that GZHMU-2 / NWF had no bacterial growth after light exposure, indicating that it had an antibacterial effect.

[0084] As shown in Figure 11, the bacterial growth on the GZHMU-2 / NWF mask shows that the colonies on the middle and inner layers of the GZHMU-2 / NWF mask after exposure to light are less than those without exposure to light.

[0085] And reference (CCS Chem.2020,2,2045-2053) synthesized JN-1 and JN-2 materials as shown in Figure 12, and the GZHMU-2 material of the present invention was compared with TiO2, ZIF-8, JN-1 and JN-2 for antibacterial testing. The results are shown in Figure 13. It can be seen that compared with other MOF materials, the GZHMU-2 material prepared by the present invention has more significant antibacterial ability. The active oxygen type was determined by EPR. As shown in Figure 14, the peak position of the EPR spectrum is consistent with OH, O2 - and 1 The characteristic peaks of O2 are consistent, among which the peak of GZHMU-2EPR spectrum is the most obvious.

Claims

1. A method for preparing a high-performance photocatalytic metal-organic framework antibacterial material, characterized in that: The steps include: Add p-toluenesulfonic acid, tris(4-aminophenyl)amine (TAPA) and Cu3L to the polyethylene glycol solution, stir and mix, then heat to react, collect the obtained precipitate by centrifugation, wash it, and dry it to obtain GZHMU-2 powder.

2. The method for preparing a high-performance photocatalytic metal organic framework antibacterial material according to claim 1, characterized in that: The mass ratio of the toluenesulfonic acid, tri(4-aminophenyl)amine and Cu3L is (4-5.5):1:(1-2).

3. The method for preparing a high-performance photocatalytic metal organic framework antibacterial material according to claim 1, characterized in that: The dosage of the polyethylene glycol PEG is a solid-liquid ratio of (30-40): 1 mg / mL; The polyethylene glycol PEG includes at least one having a MV of 200-1000.

4. The method for preparing a high-performance photocatalytic metal organic framework antibacterial material according to claim 3, characterized in that: The polyethylene glycol PEG comprises a mixture of PEG (MV: 400) and PEG (MV: 1000) in a volume ratio of (1-2): (1-2).

5. The method for preparing a high-performance photocatalytic metal organic framework antibacterial material according to claim 1, characterized in that: The temperature of the heating reaction is 150° C. to 200° C., and the time is 15 to 30 minutes.

6. The method for preparing a high-performance photocatalytic metal organic framework antibacterial material according to claim 1, characterized in that: The structure of GZHMU-2 is 7. A high-performance photocatalytic metal-organic framework antibacterial material, characterized in that: The GZHMU-2 material prepared by the preparation process described in any one of claims 1 to 6 of the metal organic framework antibacterial material has a metal organic framework structure.

8. An application of the high-performance photocatalytic metal organic framework antibacterial material according to claim 7, characterized in that: The metal organic framework antibacterial material is used to prepare antibacterial protective film material products, including masks and protective clothing.

9. The use of the high-performance photocatalytic metal organic framework antibacterial material according to claim 8, characterized in that: Its application method is: p-Toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L are added to polyethylene glycol in sequence, stirred at room temperature, and the resulting solution is evenly applied on a carrier twice, hot-pressed at high temperature, then cooled and washed with deionized water to obtain an antibacterial film rich in GZHMU-2; The solid-liquid ratio of the mixture of p-toluenesulfonic acid, tris(4-aminophenyl)amine and Cu3L to polyethylene glycol is (30-40): 1 mg / mL; The carrier comprises a non-woven fabric NWF; The high temperature hot pressing is performed at a hot pressing temperature of 150° C. to 200° C. for 15 min to 30 min.

10. The use of the high-performance photocatalytic metal organic framework antibacterial material according to claim 8, characterized in that: When the antibacterial consumable is a mask, the antibacterial film rich in GZHMU-2 is combined according to the required structure of the mask, including the following structure: The mask comprises a fixing strap, a nose clip and a mask body; The mask body has a composite layer structure consisting of a non-woven fabric outer layer, a middle layer and a non-woven fabric inner layer, wherein the middle layer is an antibacterial film rich in GZHMU-2 formed by loading on the non-woven fabric.

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